Cellulose acetate and nylon fibers containing thiorea dyesites

ABSTRACT

There is provided a process for improving the dyeability and fading resistance of fiber, comprising mixing into said fiber prior to the time it is extruded and dried from about 0.1 to about 6 percent (by weight of fiber) of a compound of the formula   WHEREIN N IS FROM 0 TO ABOUT 18, THERE BEING A DIRECT BOND BETWEEN THE NITROGEN ATOMS WHEN N IS 0.

United States Patent 2,757,190 7/1956 Jones 2,231,892 2/1941 Esselmannetal.

Primary Examiner-Theodore Morris Attorneys-Thomas J. Morgan, Stephen D. Murphy and Howard J. Greenwald ABSTRACT: There is provided a process for improving the dyeability and fading resistance of fiber, comprising mixing into said fiber prior to the time it is extruded and dried from about 0.1 to about 6 percent (by weight of fiber) of a compound of the formula wherein n is from 0 to about 18, there being a direct bond between the nitrogen atoms when n is 0.

CELLULOSE ACETATE AND NYLON FIBERS In the process of this invention from about 0.! to about 6 CONTAINING THIOREA DYESITES percent (based on the weight of the fiber) of the compound of this invention is mixed into the fiber prior to the time it is ex- This is a cohtihiiatiohih-pal' t of copending application truded and dried, although it is preferred to use from about I No- 562,512 fil July 1966 HOW abandnedto about 4 percent, and it is even more preferred to use from in Order to increase the dyeabiiity of fibers, Various addiabout 2.5 to about 3 percent. The compound may be added to tives have been incorporated via, e.g., the addition of the addih polymer b f h fib i d d, i may be dd d to tive to the polymer from which the fiber is extruded. Although h t d d fibe b f r it is dried, etc. many of these additives are effective in increasing the dyea- Whil a id variety f dyestuffs r suitable for use with biiity of the fiber, y of the fibers 50 treated exhibit P lo the shaped articles having enhanced dyeability, dyestuffs tehtioh 0t dyesthff 8")- This is due to the faCt that the which have been found to be especially suitable are dyestuffs dyestuffs undergo Changes when exposed to iiBht selected from the group consisting of acid dyestuffs and chemicais- Thus, the Presence of hiti'ogeh dioxide ozone, disperse dyestuffs. In general, however, the dyeing techniques ahd chioi'ihe ih the atmosphere encourages fadihgit is Very or the printing techniques employed should be such as to desirable to have a Process whereby both the dyeahiiity and prevent the thiourea compound which is present on or within the fading resistance of fibers is increased, and it is an object h h d i l from undergoing thennal degradation. ofthis invention to Provide-Such a P The process of this invention works well with any natural or in accordance with this ihvehtioh, there is Provided synthetic fiber. Thus, e.g., it works well with cellulose acetate Process for hi hg dyeahiiity and hiding resistance of fiber, cellulose triacetate fiber, acrylic fiber, modacrylic fiber, iihei" comprising mixing into said tihei' Phi)r to the time it is nytril fiber, olefin fiber, polyester fiber, etc. It works especially extruded and dhed from about to about 6 Percent (by well with nylon 6 fiber (which is a nylon fiber obtained by weight ofhher) compound ofthe formula polycondensation of caprolactam), triacetate fiber, and acetate fiber. When used with triacetate fiber, the process of i I 5 this invention, in addition to imparting dyeability and fading resistance, also imparts U.V. stability to the fiber. i Some of the preferred embodiments of applicant's invention (CHILI: H are presented in the examples set forth below. Unless otheri wise stated, all parts are by weight and all temperatures are in T f r f degrees centigrade. H S H H H EXAMPLES 1-4 wherein n is from O to about 18, there being a direct bond between the nitrogen atoms when n is 0. There is also prothese examples the indicated ahhhe was dissolved vided a fiber containing from about 0.1 to about 6 percent of either xyihhe or terhhryi alcohol (or mixtures f these) h the aforementioned compound; Said fiber has good dyeabmty allyl isothiocyanate was added to the amine solution in the inand f di resistance properties dicated mole ratio. Where the reaction product was a solid, it It has been discovered that a compound of the formula was removed by fiiti'atiohr Washed with y and dried- Those reaction products which were oils were obtained by H s H H H 40 evaporating the solvent from the reaction mixture. The follow 1 ll l ing table indicates the amine used, the nitrogen-substituted N- g allylthiourea compounds which result, and their melting (CHmE H points. In all cases the mole ratio of allyl isothiocyanate to 1 III amine was I. f f f f TABLE S H H H wherein n is from 0 to about 18, is effective in increasing the Amine Rmham Mcmn mm dyeability andgas fading resistance of fibers into which it is m- Ex. used compound h corporated prior to the time the fiber lS extruded and dried. Some of the compounds which work well in the process of this I Hiaminm I HNaHYL 142 invention include, e.g., a compound of the formula PLOW tiougeido) S H H H P p l H l I l 2 l,6-diaminol,6-bis(allyl- 103 |N C NC C=CH3 hexane thioureido) III hexane (CHM 3 hydrazine bis(allyl- 1x0 I H thionreido) l l 4 1.24am l,2-bis(allyl- 95 III IO II\I? CI=CHI ethane thioureido) H A H H H ethane l,l-bis(allylthiouW l,3-bis(allylthioureido) ro ane; l,8-bis(all lthioureido)octane; l,l0-bis(allylthiohrei ziwdecane; I,l2-his(allylthioureido)dodecane; l,6- whhh from about to about 3 percent (by W of bis(allylthioureido)hexane; l,l8-bis(allylthioureido)ocfiber) of the compohhds of examples F4 are hhxeh tadecane; and the like. The most effective species occur when exceheht dyhablhty ahd fad'hg resistance Properties are n is 0 (in which instance there is a direct bond between the h' to the fibers The product ofexample worked two nitrogen atoms), 3, or 6. exceedingly well The thioureas of the present invention can be prepared as il- EXAMPLE 5 lustrated, e.g., by the article of Stoutland et al. appearing in the Journal of Organic Chemistry, Vol. 24, June, I959, pp. Nylon 6 caprolactam polymer is mixed with 2 percent by 818-820. Thus, e.g., these thioureas may be prepared accordweight of the compound of example 2 and extruded. The yarn ing to the following equation: produced was drawn at a ratio of 2.99 and the denier was The preparation of some of the thioureas of this invention is ilabout 50/7. A hose leg was knitted with this yarn. A first samlustrated in the examples. ple was dyed at 60 C. for 4 minutes with 1 percent Nylomine Blue GS and 2 percent acetic acid. A second sample is dyed at 40 C. for 7 minutes with the same ingredients. A third sample was padded with l g./l. acetic acid, i g./l. rapid wetting agent RBD (an anionic surface active agent marketed by Badische Aniline and Soda Fabrik Colors and Chemicals) and 0.5 g./l. Nylomine Blue GS. In all three cases, the yarn containing the allylthiourea derivative is much deeper than the control made of nylon 6.

EXAMPLE 6 Cellulose triacetate polymer is mixed with 2 percent by weight of the compound of example 4, and extruded. The yarn produced is woven into a fabric. An identical control fabric is also produced with the exception that the control does not contain the 2 percent by weight of said compound. The control and the treated sample are then treated as follows:

a. Dyeing 1 percent Eastman Blue GP (Disperse Blue 3, Cl. No.

61,505), 1 g./l. lgepon T-l (sodium N-methyl-N-oleoyl taurate marketed by G.A.F. Corporation) 0.75 g./l. Tamol N (dispersing agent marketed by Rohm &

Hass) Run 1% hours at 95 C.

b. Printing 1.0 percent Eastman Blue GP (Disperse Blue 3, C. I. No.

61,505), 35.5 percent water 55.0 Keltex S (sodium alginate marketed by Kelco Co.) (3

percent), 8.0 percent phenyl glycol ethers 0.5 percent Basogal 0 (nonionic fatty alcohol derivative marketed by Badische Aniline and Soda Fabrik Colors and Chemicals) print-dry-stream 1 hour at p.s.i.rinse-wash.

c. Printing 1 percent Eastman Blue BGLF, 35.5 percent water 55.0 percent Keltex S 3 percent, (sodium alginate marketed by Kelco Co.), 8.0 percent phenyl glycol ethers 0.5 percent Basogal 0 (nonionic fatty alcohol derivative marketed by Badische Aniline and Soda Fabrik Colors and Chemicals) i l hour at 10 p.s.i.-rinse-wash.

In each case the samples containing the 2 percent by weight of said compound dyed a deeper shade. The samples dyed a and the samples printed b" were subjected to the A.A.T.C.C. gas chamber test while the samples printed c were subjected to the A.A.T.C.C. ozone test. The results of both tests being given in the following in the following table.

Sample Identification Ozone Fastness l cycle 2 cycles Gas Fastness l cycle 2 cycles The ozone test was conducted according to the testing procedures set forth in A.A.T.C.C. lO9-1963T. The procedure set forth in this test method is in brief an analysis wherein a treated specimen and an untreated specimen are simultaneously exposed to an atmosphere containing ozone until a control sample shows a color change corresponding to that of a standard of fading. This exposure period constitutes one cycle. Cycles are repeated from one to nine times. The control sample consists of a medium shade of gray acetate fabric prepared by dyeing in a tertiary shade with Disperse Blue 27, Disperse Red 35, and Disperse Yellow 37. The control sample is exposed until a color change, which is mainly loss of blue to that of the standard, is obtained. The standard of fading is an acetate fabric dyed with Disperse Blue 27, Disperse Red 35 and Disperse Yellow 37. The effect on color of the test specimens after three cycles and nine cycles are given by reference to the International Geometric Gray Scale wherein the readings are as follows:

Class 5Negligible or no change as shown in Gray Scale step 5.

Class 4-A change in color equivalent to Gray Scale step 4.

Class 3A change in color equivalent to Gray Scale step 3.

Class 2-A change in color equivalent to Gray Scale step 2.

Class lA change in color equivalent to Gray Scale step I The gas fading test was conducted according to the procedure set forth in A.A.T.C.C. 23-1962. The procedure set forth in this test method is in brief an analysis wherein a treated test specimen and an untreated test specimen are simultaneously exposed to a gaseous atmosphere generated by the combustion products of a gas burner until a control sample shows a color change corresponding to that of a standard of fading. The remaining portion of the procedure is similar to the ozone test which has previously been described.

As can be noted from the data given in the table, the samples containing thiourea and having the resultant deep dyeing properties, have gas fastness and ozone fading properties which are superior to similar samples which do not contain thiourea.

Although the above examples and descriptions of this invention have been very specifically illustrated, many other modifications will suggest themselves to those skilled in the art on a reading of this disclosure. These are intended to be comprehended within the scope of this invention.

What is claimed is:

1. A process for improving the dyeability and fading resistance of fiber selected from the group consisting of cellulose acetate fiber, cellulose triacetate fiber, nylon fiber, comprising the step of mixing into said fiber prior to the time it is extruded and dried from about 0.1 to about 6 percent (by weight of fiber) of a compound of the formula r f-tr S H H H wherein n is from 0 to about 18, there being a direct bond between the nitrogen atoms when n is 0.

2. The process of claim I, wherein:

a. said fiber is selected from the group consisting of cellulose triacetate fiber, cellulose acetate fiber, and nylon fiber; and

b. n is an integer from O to about 6.

3. The process of claim 2, wherein said fiber is cellulose triacetate fiber.

4. The process of claim 3, wherein n is 0.

5. The process of claim 3, wherein n is 3.

6. The process of claim 3, wherein n is 6.

7. A fiber selected from the group consisting of cellulose acetate fiber, cellulose triacetate fiber, nylon fiber, said fiber being comprised of from about 0.] to about 6 percent of the compound of claim I.

8. The fiber of claim 7, wherein n is an integer of from 0 to about 6 and said fiber is cellulose triacetate fiber.

P049) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3. 32.363 Dated January 4, 1972- In nt0 Francis S. Moussalli It is certified that. error appears in the above-identified patent and that -s a id Letters Patent are hereby corrected as shown below:

Column 1, the formula beginning atline 54 should be corrected to read N c N c c CH Column 1, line 73, after the word "equatiom" insert the following:

H N-(cH NH CH CH CH NCS HSHHH NH2 i N-g-N-c-c CH: H (CH CH PO-1Q5O UNITED STATES PATENT OFFICE 56) CERTIFICATE OF CORRECTION Patent No. 3 3,632,363 I Dated gamma I! 1912 Inventor(s) Francis S. Moussalli PAGE 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 39, before "1 hour" insert --Print-drysteam Column 3, line 60, insert the word ---test--- before the word "specimen", each occurrence.

signed and sealed this 30th day of Ma 1972.

(SEAL) Attest:

. EDWARD M.FLETCHER,' JR. ROBERT TTSGHALK Attesting Officer Commissioner of Patents 

2. The process of claim 1, wherein: a. said fiber is selected from the group consisting of cellulose triacetate fiber, cellulose acetate fiber, and nylon fiber; and b. n is an integer from 0 to about
 6. 3. The process of claim 2, wherein said fiber is cellulose triacetate fiber.
 4. The process of claim 3, wherein n is
 0. 5. The process of claim 3, wherein n is
 3. 6. The process of claim 3, wherein n is
 6. 7. A fiber selected from the group consisting of cellulose acetate fiber, cellulose triacetate fiber, nylon fiber, said fiber being comprised of from about 0.1 to about 6 percent of the compound of claim
 1. 8. The fiber of claim 7, wherein n is an integer of from 0 to about 6 and said fiber is cellulose triacetate fiber. 